Filled polyurethane or polyisocyanurate foam and method of making same

ABSTRACT

Polyurethane or polyisocyanurate foam stock and methods of manufacturing are described herein. The foam stock can include (a) a polyurethane or polyisocyanurate formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols; and (b) a filler present in an amount from greater than 50% to 90% by weight, based on the total weight of the foam stock. The density of the foam stock can be from 10 lb/ft3 to 35 lb/ft3. The flexural strength of the foam stock can be at least 100 psi. The resulting foam stock can be used to produce polyurethane or polyisocyanurate foam to be used in composite panels.

This application is a U.S. National Stage filing under 35 U.S.C. § 371of International Application No. PCT/US2016/033734, filed on May 23,2016.

FIELD OF THE DISCLOSURE

This disclosure relates generally to polyurethane or polyisocyanuratefoams, more particularly, to highly filled polyurethane orpolyisocyanurate foams.

BACKGROUND OF THE DISCLOSURE

Polymeric composites that contain organic and/or inorganic fillermaterials have become desirable for a variety of uses because of theirexcellent mechanical properties and weathering stability. In general,the superior properties of the organic-inorganic composites are achievedthrough use of the organic as a matrix material that acts as a glue withenhanced flexural properties or as a fibrous component providingreinforcement and improved tensile properties. The inorganic materialimparts various properties of rigidity, toughness, hardness, opticalappearance, interaction with electromagnetic radiation, density, andmany other physical and chemical attributes.

The use of polyurethane compositions has grown due to their superiortensile strength, impact resistance, and abrasion resistance comparedto, for example, unsaturated polyester and vinyl ester-based composites.Processes for preparing polyurethane foamed compositions are known andhave significant commercial success. However, certain problems thatoften limit application of the polyurethane foams are known to those inthe industry. For example, the processes to prepare these compositionsmay experience difficulties. Additionally, the foams may be brittle, orsuffer from poor adhesion to substrates due to the relatively high ureaconcentration that often forms on the surface of these foams. The foamsmay also be dimensionally unstable, due to a relatively high diffusioncoefficient of the carbon dioxide through the cell walls, and demoldingmay be poor due to the relatively high exothermic nature of thewater-blown reactions. Thus, there is a need for alternate polyurethanefoams with desirable mechanical properties. The compositions and methodsdescribed herein address these and other needs.

SUMMARY OF THE DISCLOSURE

Polyurethane or polyisocyanurate foam stock and methods of manufacturingare described herein. In some embodiments, the foam stock can include(a) a polyurethane or polyisocyanurate formed by the reaction of (i) oneor more isocyanates selected from the group consisting of diisocyanates,polyisocyanates, and mixtures thereof, and (ii) one or more polyols; and(b) a filler in an amount of from greater than 50% to 90% by weight,based on the total weight of the polyurethane composite, wherein duringformation of the foam stock, the reaction mixture of the one or moreisocyanates and one or more polyols is allowed to rise freely (e.g., ina mold). The density of the foam stock can be at least 10 lb/ft³. Insome cases, the density of the foam stock can be from 10 lb/ft³ to 35lb/ft³, from 10 lb/ft³ to 30 lb/ft³ or from 15 lb/ft³ to 25 lb/ft³. Theflexural strength of the foam stock can be at least 100 psi. In somecases, the flexural strength of the foam stock can be from 100 psi to700 psi.

The amount of polyurethane or polyisocyanurate in the foam stock can befrom 10% to 50% by weight, for example, 15% to 45% by weight, based onthe total weight of the foam stock. In some embodiments, the one or morepolyols can have an average hydroxyl number of from 100 to 700 mg KOH/g,from 100 to 500 mg KOH/g, or from 200 to 400 mg KOH/g. The one or morepolyols can have an average molecular weight of from 250 to 1500 g/molor from 500 to 1000 g/mol. The average functionality of the one or morepolyols can be from 2.5 to 5.5, from 3 to 5.5, or from 3 to 4. The oneor more first polyols can have an average viscosity of 150 to 5000 cPsor from 150 to 2500 cPs at 25° C. In some cases, a blend of the one ormore polyols and the one or more isocyanates used in the foams can havean average viscosity of from 100 to 6000 cPs, from 100 to 2500 cPs, orfrom 100 to 1400 cPs at 25° C.

As described above, the polyurethane or polyisocyanurate foam stock caninclude a filler. The filler can include a particulate filler and/or aplurality of fibers. The particulate filler in the foam stock caninclude coal ash such as fly ash. The amount of particulate filler inthe foam stock can be from 50 to 90% by weight, based on the totalweight of the foam stock. For example, the particulate filler can bepresent in an amount from 50% to 85% or from 60% to 80% by weight, basedon the total weight of the foam stock.

The plurality of fibers can be present in the foam stock can be from0.25% to 10% by weight, based on the total weight of the foam stock. Insome examples, the fibers can be present in an amount from 0.25% to 8%,from 0.25% to 6%, from 0.5% to 6%, or from 0.5% to 5% by weight, basedon the total weight of the foam stock. Examples of fibers useful in thefoam stock can include a plurality of glass fibers, polyalkylene fibers,polyester fibers, polyamide fibers, phenol-formaldehyde fibers,polyvinyl chloride fibers, polyacrylic fibers, acrylic polyester fibers,polyurethane fibers, polyacrylonitrile fibers, rayon fibers, cellulosefibers, carbon fibers, metal and metal-coated fibers, mineral fibers, orcombinations thereof. In some embodiments, the foam stock comprises aplurality of glass fibers. The glass fibers can have an average lengthof 1 mm or greater. In some examples, the glass fibers can have anaverage length of from 1.5 mm to 30 mm. In some embodiments, the foamstock is free of fibers.

The average thickness of the polyurethane or polyisocyanurate foam stockcan be 2 inches or greater or 2 feet or greater. In some embodiments,the average thickness of the polyurethane or polyisocyanurate foam stockcan be from 1 inch to 4 feet, from 3 inches to 4 feet, or from 2 feet to4 feet.

Methods of making the polyurethane or polyisocyanurate foam stock arealso described herein. The method can include mixing the (i) one or moreisocyanates selected from the group consisting of diisocyanates,polyisocyanates, and mixtures thereof, (ii) one or more polyols, and(iii) filler to form a mixture. The mixture may further comprise acatalyst. The mixture can include the catalyst at 0.05 to 0.5 part perhundred parts of polyol. The method can include allowing the one or moreisocyanates and the one or more polyols to react in the presence of theparticulate filler.

The polyurethane or polyisocyanurate foam stock can be formed in a mold.The mold can be a flexible, disposable container which can be removedfrom the foam by cutting through the container. For example, the moldcan be a cardboard box. The method can include applying the mixture to amold at a viscosity of from 5,000 to 100,000 cPs or from 20,000 to100,000 cPs at the temperature of the mixture. The mixture can beapplied to the mold using a nozzle traversing the mold. The mixtureapplied to the mold can have a tack free time of from 90 seconds to 7minutes or from 2 to 7 minutes. The mixture can also have a cream timeof from 20 to 120 seconds, from 40 to 120 seconds or from 80 to 120seconds.

The method of making the polyurethane or polyisocyanurate foam stock caninclude allowing the mixture to react and expand to form thepolyurethane or polyisocyanurate foam. The mixture can be allowed torise freely during foaming in the mold. In some embodiments, the foamdoes not reach a hardness of 20 shore D in less than 5 minutes or inless than 10 minutes. The method can further include cutting theresulting foam.

Foam stocks including polyurethane or polyisocyanurate and methods ofpreparing the foam stocks are described herein. The term “foam stock” asused herein, may also be referred to as a “foam,” “bun,” “bun stock,” or“foam bun stock.” The foam stock can comprise a polyurethane orpolyisocyanurate formed using reactive systems including reactiveisocyanates and reactive polyols.

Isocyanates suitable for use in the foam stock described herein includeone or more monomeric or oligomeric poly- or di-isocyanates. Themonomeric or oligomeric poly- or di-isocyanate include aromaticdiisocyanates and polyisocyanates. The isocyanates can also be blockedisocyanates or pre-polymer isocyanates. The particular isocyanate usedin the foam stock can be selected based on the desired viscosity of themixture used to form the foam stock. A low viscosity is desirable forease of handling. Other factors that influence the particular isocyanatecan include the overall properties of the foam stock, such as the amountof foaming, strength of bonding to the filler, wetting of the inorganicparticulates in the reaction mixture, strength of the resulting foam,stiffness (elastic modulus), and reactivity. Suitable isocyanatecompositions for forming the foam stock include those having viscositiesranging from 25 to 700 cPs at 25° C.

An example of a useful diisocyanate is methylene diphenyl diisocyanate(MDI). Useful MDI's include MDI monomers, MDI oligomers, and mixturesthereof. Further examples of useful isocyanates include those having NCO(i.e., the reactive group of an isocyanate) contents ranging from about25% to about 35% by weight. Examples of useful isocyanates are found,for example, in Polyurethane Handbook: Chemistry, Raw Materials,Processing Application, Properties, 2^(nd) Edition, Ed: Gunter Oertel;Hanser/Gardner Publications, Inc., Cincinnati, Ohio, which is hereinincorporated by reference. Suitable examples of aromatic polyisocyanatesinclude 2,4- or 2,6-toluene diisocyanate, including mixtures thereofp-phenylene diisocyanate; tetramethylene and hexamethylenediisocyanates; 4,4-dicyclohexylmethane diisocyanate; isophoronediisocyanate; 4,4-phenylmethane diisocyanate; polymethylenepolyphenylisocyanate; and mixtures thereof. In addition, triisocyanatesmay be used, for example, 4,4,4-triphenylmethane triisocyanate;1,2,4-benzene triisocyanate; polymethylene polyphenyl polyisocyanate;methylene polyphenyl polyisocyanate; and mixtures thereof. Suitableblocked isocyanates are formed by the treatment of the isocyanatesdescribed herein with a blocking agent (e.g., diethyl malonate,3,5-dimethylpyrazole, methylethylketoxime, and caprolactam). Isocyanatesare commercially available, for example, from Bayer Corporation(Pittsburgh, Pa.) under the trademarks MONDUR and DESMODUR. Otherexamples of suitable isocyanates include MONDUR MR Light (BayerCorporation; Pittsburgh, Pa.), PAPI 27 (Dow Chemical Company; Midland,Mich.), Lupranate M20 (BASF Corporation; Florham Park, N.J.), LupranateM70L (BASF Corporation; Florham Park, N.J.), Rubinate M (HuntsmanPolyurethanes; Geismar, La.), Econate 31 (Ecopur Industries), andderivatives thereof.

The average functionality of isocyanates useful with the foam stocksdescribed herein can be from 1.5 to 5. Further, examples of usefulisocyanates include isocyanates with an average functionality of 2 to4.5, 2.2 to 4, 2.4 to 3.7, 2.6 to 3.4, and 2.8 to 3.2.

As indicated herein, the polyurethane or polyisocyanurate foam stockincludes one or more polyols. It is generally desirable to use polyolsin liquid form, and generally in low viscosity liquid form available, asthese can be more easily mixed. Suitable polyol compositions for formingthe foam stock include those having viscosities of 5000 cPs or less at25° C. In certain embodiments, the polyol composition can include thosehaving viscosities of 4500 cPs or less, 4000 cPs or less, 3500 cPs orless, 3000 cPs or less, 2500 cPs or less, or 2000 cPs or less at 25° C.In certain embodiments, the polyol composition can include those havingviscosities of 150 cPs or greater, 250 cPs or greater, 500 cPs orgreater, 750 cPs or greater, 1000 cPs or greater, or 1500 cPs orgreater. In certain embodiments, the polyol composition can includethose having viscosities of from 150 to 5000 cPs or from 150 to 2500 cPsat 25° C. In some embodiments, a blend of the one or more polyols andthe one or more isocyanates used in the foams can have a viscosity offrom 100 to 6000 cPs, from 100 to 2500 cPs, from 100 to 1400 cPs, from100 to 1200 cPs or from 100 to 1000 cPs at 25° C.

The one or more polyols can have an average equivalent weight of 150g/eq or greater (e.g., 175 g/eq or greater, 200 g/eq or greater, 210g/eq or greater, 220 g/eq or greater, 225 g/eq or greater, or 230 g/eqor greater). In some cases, the one or more polyols have an averageequivalent weight of 700 g/eq or less (e.g., 550 g/eq or less, 500 g/eqor less, 450 g/eq or less, 400 g/eq or less, 350 g/eq or less, 300 g/eqor less, 275 g/eq or less, 250 g/eq or less, or 235 g/eq or less). Insome cases, the one or more polyols have an average equivalent weight offrom 150 g/eq to 700 g/eq, from 175 g/eq to 700 g/eq, from 200 g/eq to700 g/eq, from 150 g/eq to 500 g/eq, from 150 g/eq to 400 g/eq, or from150 g/eq to 300 g/eq. In some embodiments, the one or more polyols donot include any polyols having an equivalent weight of 750 g/eq orgreater.

In some embodiments, the one or more polyols in the polyurethane orpolyisocyanurate foam stock can include a less reactive polyol. The lessreactive polyol can have lower numbers of primary hydroxyl groups, lowerprimary hydroxyl numbers, higher numbers of secondary hydroxyl groups,and higher cream times and tack-free times in a polyurethane orpolyisocyanurate mixture, than a highly reactive polyol. In someembodiments, the one or more polyols can be capped with an alkyleneoxide group, such as ethylene oxide, propylene oxide, butylene oxide,and combinations thereof, to provide the polyols with the desiredreactivity. In some examples, the one or more polyols can include apoly(propylene oxide) polyol which contain terminal secondary hydroxylgroups and are end-capped with ethylene oxide to provide polyols withprimary hydroxyl groups.

In some embodiments, the one or more polyols have about 40% or lessprimary hydroxyl groups, about 35% or less primary hydroxyl groups,about 30% or less primary hydroxyl groups, about 25% or less primaryhydroxyl groups, about 20% or less primary hydroxyl groups, about 15% orless primary hydroxyl groups, or even about 10% or less primary hydroxylgroups. The one or more polyols can have primary hydroxyl numbers (asmeasured in units of mg KOH/g) of less than about 220, less than about200, less than about 180, less than about 160, less than about 140, lessthan about 120, less than about 100, less than about 80, less than about60, less than about 40, or even less than about 20. The number ofprimary hydroxyl groups can be determined using fluorine NMRspectroscopy as described in ASTM D4273.

The one or more polyols can have hydroxyl numbers (as measured in unitsof mg KOH/g) of 1000 or less, 900 or less, 800 or less, 700 or less, 650or less, 600 or less, 550 or less, 500 or less, 450 or less, 400 orless, 350 or less, 300 or less, 250 or less, 200 or less, or 150 orless. The one or more polyols can have hydroxyl numbers (as measured inunits of mg KOH/g) of 50 or more, 100 or more, 150 or more, 200 or more,250 or more, 300 or more, 350 or more, 400 or more, 450 or more, or 500or more. In some embodiments, the average hydroxyl number is 700 orless, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less,400 or less, 350 or less, 300 or less, or 250 or less, and/or is 100 ormore, 150 or more, 200 or more, 250 or more, 300 or more, 350 or more,400 or more, 450 or more, or 500 or more. For example, the averagehydroxyl number can be from 100-700, 100-500, 150-450, or 200-400. Insome embodiments, the one or more polyols include two or more polyols.For example, there can be a blend of 75% of a polyol having a hydroxylnumber of 400 and 25% of a polyol having a hydroxyl number of 100 toproduce an average hydroxyl number of 325.

The polyurethane or polyisocyanurate foam stock can include one or morepolyols that can provide a delay in the cream time and tack free time ofthe polyurethane or polyisocyanurate mixture during foaming. Forexample, the foam stock can include polyols containing glycerine and/oramine groups which can delay the cream time and/or tack free time of thepolyurethane or polyisocyanurate mixture. In some embodiments, the oneor more polyols can increase the cream time of the polyurethane orpolyisocyanurate mixture to 40 seconds or greater such as from 40seconds to 120 seconds. In some embodiments, the one or more polyols canincrease the tack-free time of the polyurethane or polyisocyanuratemixture to 90 seconds or greater such as from 90 seconds to 7 minutes.

The one or more polyols can include amine groups, such as primary aminegroups, secondary amine groups, tertiary amine groups, or combinationsthereof. In some embodiments, the total amine value (i.e., a measure ofthe concentration of tertiary, secondary, and primary amine groups asmeasured in units of mg KOH/g) is 50 or less, 45 or less, 40 or less, 35or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or5 or less. The one or more polyols can have a total amine value (asmeasured in units of mg KOH/g) of from 0 to 50, from greater than 0 to50, or from greater than 0 to 45.

The functionality of the one or more polyols useful with the foam stocksdescribed herein can be 7 or less, 6.5 or less, 6 or less, 5.5 or less,5 or less, 4.5 or less, 4 or less, 3.5 or less, 3.25 or less, 3 or less,2.75 or less, 2.5 or less, or 2.25 or less. In some embodiments, thefunctionality of the one or more polyols can be 2 or greater, 2.25 orgreater, 2.5 or greater, 2.75 or greater, 3 or greater, 3.25 or greater,3.5 or greater, 3.75 or greater, or 4 or greater. The averagefunctionality of the one or more polyols useful with the foam describedherein can be 5.5 or less, for example, 5 or less, 4.5 or less, 4 orless, 3.5 or less, 3.25 or less, 3 or less, 2.75 or less, 2.5 or less,or 2.25 or less. In some embodiments, the average functionality of theone or more first polyols can be 2 or greater, 2.25 or greater, 2.5 orgreater, 2.75 or greater, 3 or greater, 3.25 or greater, 3.5 or greater,3.75 or greater, or 4 or greater. Further, examples of useful firstpolyols include polyols with an average functionality of from 2.0 to5.5, from 3 to 5.5, from 3 to 5, from 3 to 4.5, from 2.5 to 4, from 2.5to 3.5, or from 3 to 4.

The one or more polyols can have an average molecular weight of 250g/mol or greater (e.g., 300 g/mol or greater, 350 g/mol or greater, 400g/mol or greater, 450 g/mol or greater, 500 g/mol or greater, 550 g/molor greater, 600 g/mol or greater, 650 g/mol or greater, 700 g/mol orgreater, 750 g/mol or greater, 800 g/mol or greater, 900 g/mol orgreater, 1000 g/mol or greater, 1200 g/mol or greater, or 1400 g/mol orgreater). In some cases, the one or more polyols have an averagemolecular weight of 1500 g/mol or less (e.g., 1400 g/mol or less, 1300g/mol or less, 1200 g/mol or less, 1100 g/mol or less, 1000 g/mol orless, 900 g/mol or less, 800 g/mol or less, 750 g/mol or less, 700 g/molor less, 650 g/mol or less, 600 g/mol or less, 550 g/mol or less, 500g/mol or less, 450 g/mol or less, 400 g/mol or less, or 300 g/mol orless). In some cases, the one or more polyols have an average molecularweight of from 250 g/mol to 1500 g/mol, from 250 g/mol to 1000 g/mol, orfrom 500 g/mol to 1000 g/mol. In some embodiments, the one or morepolyols do not include any polyols having a molecular weight of 1000g/mol or greater.

Table 1 provides a description of exemplary polyols (Polyols A-C) thatcan be used in the the polyurethane and polyisocyanurate foam stock.

TABLE 1 Properties of Polyols A-C. Properties Polyol A Polyol B Polyol CDescription Glycerine Glycerine, Sucrose, propylene diethanol amine,oxide propylene oxide Equivalent wt, g/eq 234 234 154-167 OH # (mgKOH/g) 240 240 335-365 Functionality 3 3 5.5 Ethylene oxide cap 8 25(EOC, %) Total amine value 49 (TAV, mg KOH/g) Visc (cPs @ 25° C.) 250250 2500 Cream time (s) 115 85 41 Tack-free Time (s) 240 140 375

The one or more polyols can include polyester polyols, a polyetherpolyols, or combinations thereof. Suitable polyols include polyetherpolyols such as those sold under the Carpol® trademark or under theJeffol® trademark. In some examples, the polyether polyol can include aglycerin-based polyol and derivatives thereof commercially availablefrom Carpenter Co. (e.g., Carpol® GP-240; Carpol® GP-725; Carpol®GP-700; Carpol® GP-1000; Carpol® GP-1500;). In some examples, thepolyether polyol can include a polypropylene-based polyol andderivatives thereof commercially available from Huntsman International(e.g., Jeffol® FX31-240; Jeffol® G30-650; Jeffol® FX31-167; Jeffol®A-630; Jeffol® AD-310). Suitable polyols include polyester polyolsavailable from Huntsman International (e.g., XO 13001). In someembodiments, the polyols can include a sucrose and/or amine-basedpolyol. The sucrose and/or amine-based polyol can include, for example,a polyether polyol (including for example ethylene oxide, propyleneoxide, butylene oxide, and combinations thereof) which is initiated by asucrose and/or amine group. Sucrose and/or amine-based polyols are knownin the art, and include, for example, sucrose/amine initiated polyetherpolyol sold under the trade name CARPOL® SPA-357 or CARPOL® SPA-530(Carpenter Co., Richmond, Va.) and triethanol amine initiated polyetherpolyol sold under the trade name CARPOL® TEAP-265 (Carpenter Co.,Richmond, Va.).

The polyurethane or polyisocyanurate foam stock can include one or moreadditional polyols. In some examples, the one or more additional polyolsinclude aromatic polyols such as aromatic polyester polyols, aromaticpolyether polyols, or combinations thereof, such as those sold under theTEROL® trademark (e.g., TEROL® 198 and TEROL® 250). The aromatic polyolcan have an aromaticity of 35% or greater, such as 38% or greater, 40%or greater, 45% or greater, 50% or greater, or 55% or greater and/or anaromaticity of 80% or less, 75% or less, 70% or less, 65% or less, 60%or less, 55% or less, 50% or less, 45% or less, 50% or less, 45% orless, or 40% or less.

In some embodiments, the one or more additional polyols can includepolyols having a large number of primary hydroxyl groups (e.g. 75% ormore) based on the total number of hydroxyl groups in the polyol. Forexample, the high primary hydroxyl group polyols can include 80% ormore, 85% or more, 90% or more, 95% or more, or 100% of primary hydroxylgroups.

In some embodiments, the one or more additional polyols can include aMannich polyol. Mannich polyols are the condensation product of asubstituted or unsubstituted phenol, an alkanolamine, and formaldehyde.Mannich polyols can be prepared using methods known in the art. Forexample, Mannich polyols can be prepared by premixing the phenoliccompound with a desired amount of the alkanolamine, and then slowlyadding formaldehyde to the mixture at a temperature below thetemperature of Novolak formation. At the end of the reaction, water isstripped from the reaction mixture to provide a Mannich base. See, forexample, U.S. Pat. No. 4,883,826, which is incorporated herein byreference in its entirety. The Mannich base can then be alkoxylated toprovide a Mannich polyol.

The substituted or unsubstituted phenol can include one or more phenolichydroxyl groups. In certain embodiments, the substituted orunsubstituted phenol includes a single hydroxyl group bound to a carbonin an aromatic ring. The phenol can be substituted with substituentswhich do not undesirably react under the conditions of the Mannichcondensation reaction, a subsequent alkoxylation reaction (ifperformed), or the preparation of polyurethanes from the final product.Examples of suitable substituents include alkyl (e.g., a C₁-C₁₈ alkyl,or a C₁-C₁₂ alkyl), aryl, alkoxy, phenoxy, halogen, and nitro groups.

Examples of suitable substituted or unsubstituted phenols that can beused to form Mannich polyols include phenol, o-, p-, or m-cresols,ethylphenol, nonylphenol, dodecylphenol, p-phenylphenol, variousbisphenols including 2,2-bis(4-hydroxyphenyl)propane (bisphenol A),β-naphthol, β-hydroxyanthracene, p-chlorophenol, o-bromophenol,2,6-dichlorophenol, p-nitrophenol, 4- or 2-nitro-6-phenylphenol,2-nitro-6- or 4-methylphenol, 3,5-dimethylphenol, p-isopropylphenol,2-bromo-6-cyclohexylphenol, and combinations thereof. In someembodiments, the Mannich polyol is derived from phenol or a monoalkylphenols (e.g., a para-alkyl phenols). In some embodiments, the Mannichpolyol is derived from a substituted or unsubstituted phenol selectedfrom the group consisting of phenol, para-n-nonylphenol, andcombinations thereof.

The alkanolamine used to produce the Mannich polyol can include amonoalkanolamine, a dialkanolamine, a trialkanolamine, atetraalkanolamine, or combinations thereof. Examples of suitablemonoalkanolamines include methylethanolamine, ethylethanolamine,methylisopropanolamine, ethylisopropanolamine,methyl-2-hydroxybutylamine, phenylethanolamine, ethanolamine,isopropanolamine, and combinations thereof. Suitable dialkanolaminesinclude dialkanolamines which include two hydroxy-substituted C₁-C₁₂alkyl groups (e.g., two hydroxy-substituted C₁-C₈ alkyl groups, or twohydroxy-substituted C₁-C₆ alkyl groups). The two hydroxy-substitutedalkyl groups can be branched or linear, and can be of identical ordifferent chemical composition. Examples of suitable dialkanolaminesinclude diethanolamine, diisopropanolamine, ethanolisopropanolamine,ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine,isopropanol-2-hydroxyhexylamine, ethanol-2-hydroxyhexylamine, andcombinations thereof. Suitable trialkanolamines include trialkanolamineswhich include three hydroxy-substituted C₁-C₁₂ alkyl groups (e.g., threehydroxy-substituted C₁-C₈ alkyl groups, or three hydroxy-substitutedC₁-C₆ alkyl groups). The three hydroxy-substituted alkyl groups can bebranched or linear, and can be of identical or different chemicalcomposition. Examples of suitable trialkanolamines includetriisopropanolamine (TIPA), triethanolamine,N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine (DEIPA),N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine (EDIPA),tris(2-hydroxybutyl)amine, hydroxyethyl di(hydroxypropyl)amine,hydroxypropyl di(hydroxyethyl)amine, tri(hydroxypropyl)amine,hydroxyethyl di(hydroxy-n-butyl)amine, hydroxybutyldi(hydroxypropyl)amine, and combinations thereof. Exemplarytetraalkanolamines include four hydroxy-substituted C₁-C₁₂ alkyl groups(e.g., four hydroxy-substituted C₁-C₈ alkyl groups, or fourhydroxy-substituted C₁-C₆ alkyl groups). In certain embodiments, thealkanolamine is selected from the group consisting of diethanolamine,diisopropanolamine, and combinations thereof.

Any suitable alkylene oxide or combination of alkylene oxides can beused to form the Mannich polyol. In some embodiments, the alkylene oxideis selected from the group consisting of ethylene oxide, propyleneoxide, butylene oxide, and combinations thereof. In certain embodiments,the Mannich polyol is alkoxylated with from 100% to about 80% propyleneoxide and from 0 to about 20 wt % ethylene oxide.

Mannich polyols are known in the art, and include, for example, ethyleneand propylene oxide-capped Mannich polyols sold under the trade namesCARPOL® MX-425 and CARPOL® MX-470 (Carpenter Co., Richmond, Va.).

In some embodiments, the reaction mixture can include one or moreadditional isocyanate-reactive monomers such as one or more polyamines.Suitable polyamines can correspond to the polyols described herein (forexample, a polyester polyol or a polyether polyol), with the exceptionthat the terminal hydroxy groups are converted to amino groups, forexample by amination or by reacting the hydroxy groups with adiisocyanate and subsequently hydrolyzing the terminal isocyanate groupto an amino group. By way of example, the polyamine can be polyetherpolyamine, such as polyoxyalkylene diamine or polyoxyalkylene triamine.Polyether polyamines are known in the art, and can be prepared bymethods including those described in U.S. Pat. No. 3,236,895 to Lee andWinfrey. Exemplary polyoxyalkylene diamines are commercially available,for example, from Huntsman Corporation under the trade names Jeffamine®D-230, Jeffamine® D-400 and Jeffamine® D-2000. Exemplary polyoxyalkylenetriamines are commercially available, for example, from HuntsmanCorporation under the trade names Jeffamine® T-403, Jeffamine® T-3000,and Jeffamine® T-5000.

In some embodiments, the reaction mixture can include an alkoxylatedpolyamine (i.e., alkylene oxide-capped polyamines) derived from apolyamine and an alkylene oxide. Alkoxylated polyamines can be formed byreacting a suitable polyamine with a desired number of moles of analkylene oxide. Suitable polyamines include monomeric, oligomeric, andpolymeric polyamines. In some cases, the polyamines has a molecularweight of less than 1000 g/mol (e.g., less than 800 g/mol, less than 750g/mol, less than 500 g/mol, less than 250 g/mol, or less than 200 lessthan 200 g/mol). Examples of suitable polyamines that can be used toform alkoxylated polyamines include ethylenediamine, 1,3-diaminopropane,putrescine, cadaverine, hexamethylenediamine, 1,2-diaminopropane,o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, spermidine,spermine, norspermidine, toluene diamine, 1,2-propane-diamine,diethylenetriamine, triethylenetetramine, tetraethylene-pentamine(TEPA), pentaethylenehexamine (PEHA), and combinations thereof. Anysuitable alkylene oxide or combination of alkylene oxides can be used tocap the polyamine. In some embodiments, the alkylene oxide is selectedfrom the group consisting of ethylene oxide, propylene oxide, butyleneoxide, and combinations thereof. Alkylene oxide-capped polyamines areknown in the art, and include, for example, propylene oxide-cappedethylene diamine sold under the trade name CARPOL® EDAP-770 (CarpenterCo., Richmond, Va.) and ethylene and propylene oxide-capped ethylenediamine sold under the trade name CARPOL® EDAP-800 (Carpenter Co.,Richmond, Va.).

The additional isocyanate-reactive monomer (when used) can be present invarying amounts relative the one or more polyols used to form the foamstock. In some embodiments, the additional isocyanate-reactive monomercan be present in an amount of 30% or less, 25% or less, 20% or less,15% or less, 10% or less, or 5% or less by weight based on the weight ofthe one or more polyols.

As indicated herein, in the polyurethane or polyisocyanurate foams, oneor more isocyanates are reacted with the one or more polyols (and anyadditional isocyanate-reactive monomers) to produce the polyurethane orpolyisocyanurate formulation. In general, with regards to thepolyurethane formulation, the ratio of isocyanate groups to the totalisocyanate reactive groups, such as hydroxyl groups, water and aminegroups, is in the range of about 0.5:1 to about 1.5:1, which whenmultiplied by 100 produces an isocyanate index between 50 and 150.Additionally, the isocyanate index can be from about 80 to about 120,from about 90 to about 120, from about 100 to about 115, or from about105 to about 110. With regards to the polyisocyanurate formulation, theisocyanate index can be from 180 to 380, for example, from 180 to 350,from 200 to 350, or from 200 to 270. As used herein, an isocyanate maybe selected to provide a reduced isocyanate index, which can be reducedwithout compromising the chemical or mechanical properties of the foamstock.

One or more catalysts can be added to facilitate curing and can be usedto control the curing time of the polyurethane or polyisocyanuratematrix. Examples of useful catalysts include amine-containing catalysts(including tertiary amines such as DABCO and tetramethylbutanediamine,and diethanolamine) and tin-, mercury-, and bismuth-containingcatalysts. In some embodiments, the catalyst includes a delayed-actiontin catalyst. In some embodiments, 0.01 wt % to 2 wt % catalyst orcatalyst system (e.g., 0.025 wt % to 1 wt %, 0.05 wt % to 0.5 wt %, or0.1 wt % to about 0.25 wt %) can be used based on the weight of thepolyurethane or polyisocyanurate. In some embodiments, 0.05 to 0.5 partscatalyst or catalyst system per hundred parts of polyol can be used.

The polyurethane or polyisocyanurate can be present in the foam stock inamounts from 10% to 50% based on the weight of the foam stock. Forexample, the polyurethane or polyisocyanurate can be included in anamount from 14% to 50% or 20% to 50% by weight, based on the weight ofthe foam stock. In some embodiments, the polyurethane orpolyisocyanurate can be present in an amount of 10% or greater, 15% orgreater, 20% or greater, 25% or greater, 30% or greater, 35% or greater,40% or greater, or 45% or greater by weight, based on the weight of thefoam stock. In some embodiments, the polyurethane or polyisocyanuratecan be present in an amount of 50% or less, 45% or less, 40% or less,35% or less, 30% or less, 25% or less, 20% or less, or 15% or less byweight, based on the weight of foam stock.

The polyurethane or polyisocyanurate foam stock can include a filler.The filler can be described by its aspect ratio. In some embodiments,the filler in the foam can have an average aspect ratio of length todiameter of from 1:1 to 6000:1. For example, the filler can have anaverage aspect ratio of from 1:1 to 5000:1, 1:1 to 4000:1, 1:1 to3000:1, 1:1 to 2000:1, 1:1 to 1000:1, 1:1 to 700:1, 1:1 to 500:1, 1:1 to250:1, 1.05:1 to 400:1, 1.1:1 to 300:1, 1.15:1 to 250:1, or 1.2:1 to200:1. In some embodiments, the filler can have an average aspect ratioof length to diameter of 200:1 or less, 150:1 or less, 100:1 or less,75:1 or less, 50:1 or less, 40:1 or less, 30:1 or less, 20:1 or less,10:1 or less, or 5:1 or less, and from 1:1 or more (e.g., 1.05:1 ormore, 1.1:1 or more, 1.15:1 or more, or 1.2:1 or more).

The filler can include a particulate filler and particularly aninorganic particulate filler. Suitable examples of particulate fillerscan be an ash, ground/recycled glass (e.g., window or bottle glass);milled glass; glass spheres; glass flakes; activated carbon; calciumcarbonate; aluminum trihydrate (ATH); silica; sand; ground sand; silicafume; slate dust; crusher fines; red mud; amorphous carbon (e.g., carbonblack); clays (e.g., kaolin); mica; talc; wollastonite; alumina;feldspar; bentonite; quartz; garnet; saponite; beidellite; granite;slag; calcium oxide; calcium hydroxide; antimony trioxide; bariumsulfate; magnesium oxide; titanium dioxide; zinc carbonate; zinc oxide;nepheline syenite; perlite; diatomite; pyrophillite; flue gasdesulfurization (FGD) material; soda ash; trona; expanded clay; expandedshale; expanded perlite; vermiculite; volcanic tuff; pumice; hollowceramic spheres; hollow plastic spheres; expanded plastic beads (e.g.,polystyrene beads); ground tire rubber; and mixtures thereof.

The particulate filler can have a median particle size diameter of from0.2 micron to 100 microns. For example, the particulate filler can havea median particle size diameter of 100 microns or less, 95 microns orless, 90 microns or less, 85 microns or less, 80 microns or less, 75microns or less, 70 microns or less, 65 microns or less, 60 microns orless, 55 microns or less, 50 microns or less, 45 microns or less, 40microns or less, 35 microns or less, 30 microns or less, or 25 micronsor less. In some embodiments, the particulate filler can have a medianparticle size diameter of 0.2 microns or more, 0.3 microns or more, 0.4microns or more, 0.5 microns or more, 0.7 microns or more, 1 micron ormore, 2 microns or more, 5 microns or more, 10 microns or more, 15microns or more, 20 microns or more, 25 microns or more, 30 microns ormore, 35 microns or more, 40 microns or more, or 45 microns or more. Insome examples, the particulate filler can have a median particle sizediameter of from 0.2 microns to 100 microns, 0.2 microns to 90 microns,or 0.3 microns to 80 microns, 1 to 50 microns, 1 to 25 microns, or 5 to15 microns.

In some embodiments, the particulate filler includes an ash. The ash canbe a coal ash or another type of ash such as those produced by firingfuels including industrial gases, petroleum coke, petroleum products,municipal solid waste, paper sludge, wood, sawdust, refuse derivedfuels, switchgrass or other biomass material. The coal ash can be flyash, bottom ash, or combinations thereof. In some examples, theparticulate filler includes fly ash. Fly ash is produced from thecombustion of pulverized coal in electrical power generating plants. Thefly ash useful with the foam stock described herein can be Class C flyash, Class F fly ash, or a mixture thereof. Fly ash produced bycoal-fueled power plants is suitable for incorporation in the foamstocks described herein. In some embodiments, the particulate fillerconsists of or consists essentially of fly ash.

The fly ash can have a particle size distribution with at least twomodes. For example, the particle size distribution of the fly ash can bethree, four, five, or more modes. Alternatively, the fly ash can beblended with another fly ash to modify the properties of the fly ash toproduce a fly ash having a particle size distribution with at leastthree modes.

In some embodiments, the fly ash can include a first mode having amedian particle diameter of 2.0 microns or less. In some examples, themedian particle size of the first mode can be 0.3 microns to 1.5microns, 0.4 microns to 1 microns, or 0.5 microns to 0.8 microns (e.g.,0.7 microns). The fly ash can include a second mode having a medianparticle diameter of from 3 microns to less than 40 microns. In someexamples, the median particle size of the second mode can be from 5microns to 35 microns, 10 microns to 30 microns, or 10 microns to 25microns. The fly ash can include a third mode having a median particlediameter of 40 microns or greater. In some examples, the median particlesize of the third mode can be from 40 microns to less than 100 microns,for example from 40 microns to 90 microns, 40 microns to 80 microns, orfrom 40 microns to 75 microns. In some embodiments, the fly ash caninclude a first mode having a median particle diameter of from 0.3microns to 1.0 micron, a second mode having a median particle diameterof from 10 microns to 25 microns, and a third mode having a medianparticle diameter of from 40 microns to 80 microns. In some examples,the fly ash can also include an additional ultrafine mode with a medianparticle diameter of from 0.05 microns to 0.2 microns.

In some embodiments, the particle size distribution can include 11-35%of the particles by volume in the first mode, 65-89% of the particles byvolume in the second mode. In some embodiments, the particle sizedistribution can include 11-17% of the particles by volume in the firstmode, 56-74% of the particles by volume in the second mode, and 12-31%of the particles by volume in the third mode. The ratio of the volume ofparticles in the second mode to the volume of particles in the firstmode can be from 4.5 to 7.5.

The particulate filler can be present in the foam stock described hereinin amounts from 35% to 90% by weight. Examples of the amount ofparticulate filler present in the foam stock described herein include35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%,49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%,63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%,77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%by weight. In some embodiments, the particulate filler, for example flyash, can be present in amounts from 50% to 80% by weight such as from55% to 80% by weight or from 60% to 75% by weight.

In some embodiments, the particulate filler can include fly ash andcalcium carbonate. When used with fly ash, the amount of calciumcarbonate in the foam stock can be from 0.1% to 15% by weight, based onthe weight of the foam stock. In some embodiments, the foam stock caninclude 15% or less, 14% or less, 12% or less, 10% or less, or 8% orless by weight calcium carbonate. In some embodiments, the foam stockcan include 0.1% or greater, 0.5% or greater, 1% or greater, 2% orgreater, 3% or greater, or 5% or greater by weight calcium carbonate. Insome embodiments, when used with fly ash, the foam stock can include 1%to 15%, 1% to 10%, or 1% to 8% by weight calcium carbonate.

In some embodiments, the particulate filler can include an organicfiller, such as a recycled polymeric material. Suitable examples includepulverized polymeric foam or recycled rubber material.

The filler can include a plurality of fibers. The fibers can be anynatural or synthetic fiber, based on inorganic or organic materials.Inorganic and organic fibers suitable for use with the foam stock caninclude glass fibers, basalt fibers, alumina silica fibers, aluminumoxide fibers, silica fibers, carbon fibers, metal fibers, metal andmetal-coated fibers, mineral fibers (such as stone wool, slag wool, orceramic fiber wool), polyalkylene fibers, polyester fibers, polyamidefibers, phenol-formaldehyde fibers, polyvinyl chloride fibers,polyacrylic fibers, acrylic polyester fibers, polyurethane fibers,polyacrylonitrile fibers, rayon fibers, cellulose fibers, carbon fibers,or combinations thereof. In certain embodiments, the fiber material caninclude hemp fibers, sisal fibers, cotton fibers, straw, reeds, or othergrasses, jute, bagasse fibers, bamboo fibers, abaca fibers, flax,southern pine fibers, wood fibers, cellulose, saw dust, wood shavings,lint, vicose, leather fibers, rayon, and mixtures thereof. Othersuitable fibers include synthetic fibers such as, Kevlar, viscosefibers, Dralon R fibers, polyethylene fibers, polyethylene terephthalatefibers, polyethylene naphthalate fibers, polypropylene fibers, polyvinylalcohol fibers, aramid fibers, or combinations thereof. In someembodiments, the fiber material can include glass fibers. Glass fiberscan include fibrous glass such as E-glass, C-glass, S-glass, andAR-glass fibers. In some examples, fire resistant or retardant glassfibers can be included to impart fire resistance or retarding propertiesto the foam stock. In some embodiments, the foam stock can include acombination of fibers that break and fibers that do not break when thefoam stock is being formed using processing machinery and/or fracturedby external stress.

In some embodiments, the fibers can be dispersed within the foam stock.The fibers in the foam stock can be present in the form of individualfibers, chopped fibers, bundles, strings such as yarns, fabrics, papers,rovings, mats, or tows. In some embodiments, the foam stock can includea plurality of glass fibers. The average length of the glass fibers inthe foam stock can be 1 mm or greater, 1.5 mm or greater, 2 mm orgreater, 3 mm or greater, 4 mm or greater, 5 mm or greater, or 6 mm orgreater. In some embodiments, the average length of the glass fibers canbe 50 mm or less, 40 mm or less, 30 mm or less, 20 mm or less, 15 mm orless, 12 mm or less, or 10 mm or less. In some examples, the glassfibers can be from 1 mm to 50 mm in average length. For example, theglass fibers can be from 1.5 mm to 30 mm, from 2 mm to 30 mm, from 3 mmto 30 mm, or from 3 mm to 15 mm in average length. The glass fibers inthe foam stock can have any dimension of from 1 μm to 30 μm in averagediameter. For example, the average diameter of the glass fibers can be1.5 μm to 30 μm, 3 μm to 20 μm, 4 μm to 18 μm, or 5 μm to 15 μm inaverage diameter. The glass fibers can be provided in provided in thefoam stock in a random orientation or can be axially oriented.

The fibers can also be described by its aspect ratio. In someembodiments, the fibers in the foam stock can have an average aspectratio of length to diameter of from 8:1 to 4000:1. For example, thefibers can have an average aspect ratio of from 5:1 to 2000:1, 5:1 to1500:1, 5:1 to 1000:1, 5:1 to 750:1, 1.5:1 to 500:1, 1.5:1 to 400:1,1.5:1 to 300:1, 1.5:1 to 250:1, 2:1 to 200:1, 2.5:1 to 150:1, 3:1 to100:1, 3.5:1 to 75:1, 4:1 to 50:1, 5:1 to 25:1, 5:1 to 20:1, or 5:1 to10:1. In some embodiments, the fibers can have an average aspect ratioof length to diameter of 1.5:1 or greater, 2:1 or greater, 3:1 orgreater, 4:1 or greater, 5:1 or greater, 7.5:1 or greater, 10:1 orgreater, 15:1 or greater, 20:1 or greater, 25:1 or greater, 30:1 orgreater, or 40:1 or greater. In some embodiments, the fiber can have anaverage aspect ratio of length to diameter of 200:1 or less, 150:1 orless, 100:1 or less, 75:1 or less, 50:1 or less, 40:1 or less, 30:1 orless, 20:1 or less, 10:1 or less, or 5:1 or less.

The fibers (when used) can be present in the foam stock in amounts of15% or less by weight, based on the weight of foam stock. For example,the fibers can be present in amounts from 0.25% to 15%, 0.5% to 15%, 1%to 15%, 0.25% to 10%, 0.5% to 10%, 1% to 10%, 0.25% to 8%, 0.25% to 6%,or 0.25% to 4% by weight, based on the weight of the foam stock. In someembodiments, the foam stock is free of fibers dispersed within the foamstock.

The foam stock described herein can comprise additional materials. Theadditional materials useful with the foam stock can include foamingagents, blowing agents, surfactants, chain-extenders, crosslinkers,coupling agents, UV stabilizers, fire retardants, antimicrobials,anti-oxidants, and pigments. Though the use of such components is wellknown to those of skill in the art, some of these additional additivesare further described herein.

Chemical foaming agents include azodicarbonamides (e.g., Celogenmanufactured by Lion Copolymer Geismar); and other materials that reactat the reaction temperature to form gases such as carbon dioxide. In thecase of polyurethane and polyisocyanurate foam, water is an exemplaryfoaming agent that reacts with isocyanate to yield carbon dioxide. Thepresence of water as an added component or in the filler also can resultin the formation of polyurea bonds through the reaction of the water andisocyanate. In some embodiments, water may be present in the mixtureused to produce the foam stock in an amount of from greater than 0% to5% by weight or less, based on the weight of the mixture. In someembodiments, water can be present in a range of 0.02% to 4%, 0.05% to3%, 0.1% to 2%, or 0.2% to 1% by weight, based on the weight of themixture. In some embodiments, the mixture used to produce the foam stockincludes less than 0.5% by weight water. In some embodiments, nochemical foaming agents are used. In some embodiments, water is the onlyfoaming agent used.

Surfactants can be used as wetting agents and to assist in mixing anddispersing the materials in a foam. Surfactants can also stabilize andcontrol the size of bubbles formed during the foaming event and theresultant cell structure. Surfactants can be used, for example, inamounts below about 0.5 wt % based on the total weight of the mixture.Examples of surfactants useful with the polyurethanes described hereininclude anionic, non-ionic and cationic surfactants. For example,silicone surfactants such as Tegostab B-8870, DC-197 and DC-193 (AirProducts; Allentown, Pa.) can be used.

Low molecular weight reactants such as chain-extenders and/orcrosslinkers can be included in the foam stock described herein. Thesereactants help the foam stock to distribute and contain the fibermaterial and/or particulate filler within the composite. Chain-extendersare difunctional molecules, such as diols or diamines, that canpolymerize to lengthen the urethane polymer chains. Examples ofchain-extenders include ethylene glycol; 1,4-butanediol; ethylenediamine, 4,4′-methylenebis(2-chloroaniline) (MBOCA); diethyltoluenediamine (DETDA); and aromatic diamines such as Unilink 4200(commercially available from UOP). Crosslinkers are tri- or greaterfunctional molecules that can integrate into a polymer chain through twofunctionalities and provide one or more further functionalities (i.e.,linkage sites) to crosslink to additional polymer chains. Examples ofcrosslinkers include glycerin, trimethylolpropane, sorbitol,diethanolamine, and triethanolamine. In some foam stock, a crosslinkeror chain-extender may be used to replace at least a portion of the oneor more polyols in the foam stock. For example, the polyurethane orpolyisocyanurate can be formed by the reaction of an isocyanate, apolyol, and a crosslinker.

Coupling agents and other surface treatments such as viscosity reducers,flow control agents, or dispersing agents can be added directly to thefiller or fiber, or incorporated prior to, during, and/or after themixing and reaction of the foam stock. Coupling agents may also reducethe viscosity of the foam stock mixture. Coupling agents can also allowhigher filler loadings of the particulate filler such as fly ash, and/orfiber material, and may be used in small quantities. For example, thefoam stock may comprise about 0.01 wt % to about 0.5 wt % of a couplingagent. Examples of coupling agents useful with the foam stock describedherein include Ken-React LICA 38 and KEN-React KR 55 (KenrichPetrochemicals; Bayonne, N.J.). Examples of dispersing agents usefulwith the foam stock described herein include JEFFSPERSE X3202,JEFFSPERSE X3202RF, and JEFFSPERSE X3204 (Huntsman Polyurethanes;Geismar, La.).

Ultraviolet light stabilizers, such as UV absorbers, can be added to thefoam stock described herein. Examples of UV light stabilizers includehindered amine type stabilizers and opaque pigments like carbon blackpowder. Fire retardants can be included to increase the flame or fireresistance of the foam stock. Antimicrobials can be used to limit thegrowth of mildew and other organisms on the surface of the composite.Antioxidants, such as phenolic antioxidants, can also be added.Antioxidants provide increased UV protection, as well as thermaloxidation protection.

Pigments or dyes can optionally be added to the foam stock describedherein. An example of a pigment is iron oxide, which can be added inamounts ranging from about 2 wt % to about 7 wt %, based on the totalweight of the foam stock.

The polyurethane or polyisocyanurate foam stock can have a thickness (zdirection) of 1 inch to 4 feet. For example, for foam stock that can befurther subdivided into units having thicknesses of 2 inches or less(e.g., ¼ inch to 1 inch), the foam stock can have a thickness of from 3inches to 4 feet. For example, the foam stock can have an averagethickness of 3 inches or greater, 4 inches or greater, 6 inches orgreater, 1 foot or greater, 2 feet or greater, 2.5 feet or greater, 3feet or greater, 3.5 feet or greater, or 4 feet or greater. In someembodiments, the foam stock can have an average thickness of from 3inches to 4 feet, 3 inches to 6 inches, 1 foot to 4 feet, or 2 feet to 3feet.

The polyurethane or polyisocyanurate foam stock can have a length andwidth (x and y direction) of 2 feet or greater and from 2 feet to 4feet, respectively. For example, the polyurethane or polyisocyanuratefoam stock can have a length of 2 feet or greater, 5 feet or greater, 10feet or greater, or it can be produced with a continuous length. Thepolyurethane or polyisocyanurate foam stock can have a width of 2 feetto 4 feet, or from 2 to 3 feet.

As described herein, the polyurethane or polyisocyanurate foam stock cancomprise a high filler loading, such as from 50% to 90% by weight of thefoam stock, which can result in an increase in the density of the foamstock. In some embodiments, it is desirable that the foam stock has adensity below a particular threshold at the desired loadings so itremains relatively lightweight and/or can be effectively processed. Insome embodiments, the amount of fibers and/or particulate filler can bepresent in the composite mixture in amounts to produce a foam stockhaving a density of 35 lb/ft³ or less. For example, the density of thefoam stock can be 10 lb/ft³ to 35 lb/ft³, 15 lb/ft³ to 35 lb/ft³, 15lb/ft³ to 25 lb/ft³, 10 lb/ft³ to 30 lb/ft³, 10 lb/ft³ to 25 lb/ft³, or20 lb/ft³ to 30 lb/ft³. In some embodiments, the density of the foamstock is at least 10 lb/ft³.

Incorporation of the fibers and/or particulate filler in a high fillerloading can increase the flexural strength of the foam stock, comparedto a foam stock without the fibers and/or high particulate filler. It isdesirable to provide polyurethane and polyisocyanurate foams that arerelatively lightweight and strong enough to be used in variousapplications such as by itself as a structural material or in place ofcomposite boards or the like. In some embodiments, the flexural strengthof the polyurethane or polyisocyanurate foam stock can be increased byat least 10%, for example, 15% or greater, 20% or greater, 25% orgreater, 30% or greater, 35% or greater, 50% or greater, 75% or greater,or even 100% or greater, compared to a foam stock without fibers and/orparticulate filler. The flexural strength of the foam stock describedherein can be 100 psi or greater. For example, the flexural strength ofthe foam stock can be 200 psi or greater, 300 psi or greater, 400 psi orgreater, 500 psi or greater, 600 psi or greater, or 700 psi or greater.In some embodiments, the flexural strength of the foam stock can be from100 to 700 psi. The flexural strength can be determined by the loadrequired to fracture a rectangular prism loaded in the three point bendtest as described in ASTM C1185-08 (2012).

The foam stock can exhibit a ratio of flexural strength (in psi) todensity (in lb/ft³) of from 10:1 to 200:1. In some embodiments, the foamstock can exhibit a ratio of flexural strength (in psi) to density (inlb/ft³) of from 10:1 to 100:1 or from 20:1 to 100:1.

The modulus of elasticity (stiffness) of the foam stock can be 10 ksi orgreater, 15 ksi or greater, 20 ksi or greater, 25 ksi or greater, or 30ksi or greater. For example, the modulus of elasticity can be from 15 to30 ksi, from 20 to 30 ksi, or from 22 to 28 ksi. The modulus ofelasticity can be determined as described in ASTM C947-03.

The foam stock can exhibit a ratio of modulus of elasticity (in ksi) todensity (in lb/ft³) of from 1:2 to 2:1. In some embodiments, the foamstock can exhibit a ratio of modulus of elasticity (in ksi) to density(in lb/ft³) of 1:1.5 to 1.5:1 or from 1:1.2 to 1.2:1.

The compressive strength of the foam stock can be 100 psi or greater.For example, the compressive strength can be from 100 to 300 psi, from150 to 250 psi or from 175 to 240 psi. The compressive strength can bedetermined as described in ASTM D1621. The foam stock can exhibit aratio of compressive strength (in psi) to density (in lb/ft³) of from7:1 to 25:1. In some embodiments, the foam stock can exhibit a ratio ofcompressive strength (in psi) to density (in lb/ft³) of from 8:1 to15:1.

Reinforced polyurethane and polyisocyanurate foam stocks Compositepanels comprising the polyurethane and polyisocyanurate foam stock aredescribed herein. In some embodiments, the composite panel can include afirst fiber reinforcement; a polyurethane or polyisocyanurate foam stockhaving a first surface and a second surface opposite the first surface,wherein the first surface is in contact with the first fiberreinforcement; and a cementitious material adjacent the first fiberreinforcement opposite the foam stock.

The fiber reinforcement can include any of the fiber materials asdescribed herein and can include a blend of different fibers (eithertype or size). In some embodiments, the fiber reinforcement can includeglass fibers. In some embodiments, the fibrous glass is a low alkalinityfiber such as an E-glass fiber. The fiber reinforcement can be woven ornon-woven. In some embodiments, the fiber reinforcement can be presentin the form of individual fibers, chopped fibers, bundles, strings suchas yarns, fabrics, scrims, papers, rovings, mats, or tows.

The fibers in the reinforcement can have an average diameter of 100microns or less. For example, the fibers in the fiber reinforcement canhave an average diameter of 1 μm or greater, 2 μm or greater, 3 μm orgreater, 4 μm or greater, 5 μm or greater, 10 μm or greater, 15 μm orgreater, 20 μm or greater, 25 μm or greater, 30 μm or greater, 40 μm orgreater, 50 μm or greater, 60 μm or greater, 70 μm or greater, 80 μm orgreater, 90 μm or greater, or 100 μm or greater. In some embodiments,the fibers in the fiber reinforcement can have an average diameter of 90μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less,40 μm or less, 30 μm or less, 25 μm or less, or 20 μm or less. Incertain embodiments, the fibers in the fiber reinforcement can have anaverage diameter of from 1 μm to 100 μm, 1 μm to 70 μm, 1 μm to 50 μm, 1μm to 25 μm, 5 μm to 100 μm, 5 μm to 50 μm, 5 μm to 25 μm, or 5 μm to 20μm.

The thickness of the fiber reinforcement on the foam stock can be anysuitable thickness to reinforce the foam stock. In some embodiments, theaverage thickness of the fiber reinforcement can be 0.1 inch or less.For example, the fiber reinforcement can have an average thickness of0.07 inch or less, 0.05 inch or less, 0.03 inch or less, 0.01 inch orless, 0.005 inch or less, or 0.001 inch or less. In some embodiments,the fiber reinforcement can have an average thickness of 0.001 inch orgreater, 0.005 inch or greater, 0.01 inch or greater, 0.03 inch orgreater, 0.05 inch or greater, or 0.07 inch or greater. In someembodiments, the fiber reinforcement can have an average thickness offrom 0.001 inch to 0.1 inch or from 0.001 inch to 0.05 inch.

The fiber reinforcement can have a basis weight of 50 g/ft² or less. Insome embodiments, the fiber reinforcement can have a basis weight of 40g/ft² or less, 30 g/ft² or less, 20 g/ft² or less, 17 g/ft² or less, 15g/ft² or less, 12 g/ft² or less, 10 g/ft² or less, 9 g/ft² or less, 8g/ft² or less, 7 g/ft² or less, 6 g/ft² or less, or 5 g/ft² or less. Insome embodiments, the fiber reinforcement can have a basis weight of 0.5g/ft² or greater, 1 g/ft² or greater, 2 g/ft² or greater, 3 g/ft² orgreater, 4 g/ft² or greater, 5 g/ft² or greater, 7 g/ft² or greater, 10g/ft² or greater, 15 g/ft² or greater, or 20 g/ft² or greater. In someembodiments, the fiber reinforcement can have a basis weight of from 0.5g/ft² to 50 g/ft², from 0.5 g/ft² to 25 g/ft², from 0.5 g/ft² to 20g/ft², from 1 g/ft² to 10 g/ft², or from 1.5 g/ft² to 10 g/ft².

As described herein, the composite panel can include a cementitiousmaterial. In some embodiments, the cementitious material can form alayer adjacent the first fiber reinforcement, opposite the foam stock.The cementitious material can include any suitable material for forminga cementitious layer with the desirable properties. In some embodiments,the cementitious material includes a rapid set cement. The rapid setcement can include calcium aluminate cement (CAC), calcium phosphatecement, calcium sulfate hydrate, calcium sulfoaluminate (CSA) cement,magnesium oxychloride cement, magnesium oxysulfate cement, magnesiumphosphate cement, or combinations thereof. In some embodiments, thecementitious material can include Portland cement. The rapid set cementand/or the Portland cement can be present in an amount of 50% or greaterby weight, e.g., 60% or greater, 70% or greater, 80% or greater, or 90%or greater by weight, based on the total weight of the cementitiousmaterial. In some embodiments, the cementitious material does notinclude gypsum (calcium sulfate hydrate).

In some embodiments, the cementitious material can include an inorganicpolymer formed by reacting a reactive powder and an activator in thepresence of water. Suitable inorganic polymers are described in U.S.Patent Publication No. 2014/0349104, which is herein incorporated byreference. In some embodiments, the reactive powder for use in thecementitious material includes fly ash. In some examples, the majorityof the fly ash present is Class C fly ash (i.e., greater than 50% of thefly ash present is Class C fly ash).

The fly ash is the principal component of the reactive powder and can bepresent in an amount of greater than 50% by weight, 65% by weight orgreater, 75% by weight or greater, or 85% by weight or greater of thereactive powder. In some examples, the fly ash is present in an amountof 90% by weight or greater of the reactive powder or 95% by weight orgreater of the reactive powder. For example, the fly ash can be presentin an amount of 85% by weight or greater, 86% by weight or greater, 87%by weight or greater, 88% by weight or greater, 89% by weight orgreater, 90% by weight or greater, 91% by weight or greater, 92% byweight or greater, 93% by weight or greater, 94% by weight or greater,95% by weight or greater, 96% by weight or greater, 97% by weight orgreater, 98% by weight or greater, or 99% by weight or greater based onthe weight of the reactive powder. In some embodiments, the reactivepowder consists of or consists essentially of fly ash.

The reactive powder for use as a reactant to form the inorganic polymercompositions can further include other cementitious components. In someembodiments, the reactive powder can include a rapid set cement asdescribed herein. In some embodiments, the reactive powder can includePortland cement. In some embodiments, the reactive powder furtherincludes slag. In some embodiments, the reactive powder further includessand. In some embodiments, the reactive powder includes Portland cement,calcium aluminate cement, calcium sulfoaluminate cement, and/or slag. Inthese examples, the reactive powder can include 10% or less by weight ofthe other cementitious material. In some examples, the reactive powderincludes 5% by weight or less, 3% by weight or less, or 1% by weight orless of other cementitious material. For example, the reactive powdercan include the other cementitious material cement in an amount of 10%or less by weight, 9% or less by weight, 8% or less by weight, 7% orless by weight, 6% or less by weight, 5% or less by weight, 4% or lessby weight, 3% or less by weight, 2% or less by weight, 1% or less byweight, or 0.5% or less by weight. In some examples, the reactive powderis substantially free from other cementitious material. For example, thereactive powder can include less than 0.1% by weight, less than 0.01% byweight, or less than 0.001% by weight of Portland cement based on theweight of the reactive powder. In some embodiments, the reactive powderincludes no Portland cement.

The reactive powder can also include a ground slag such as blast furnaceslag in an amount of 10% or less by weight. For example, the reactivepowder can include slag in an amount of 10% or less, 9% or less, 8% orless, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% orless, or 1% or less by weight.

An activator is a further reactant used to form the inorganic polymercompositions described herein. The activator allows for rapid setting ofthe inorganic polymer compositions and also imparts compressive strengthto the compositions. The activator can include one or more of acidic,basic, and/or salt components. For example, the activator can includecitrates, hydroxides, metasilicates, carbonates, aluminates, sulfates,and/or tartrates. The activator can also include other multifunctionalacids that are capable of complexing or chelating calcium ions (e.g.,EDTA). Specific examples of suitable citrates for use as activatorsinclude citric acid and its salts, including, for example, sodiumcitrate and potassium citrate. Specific examples of suitable tartratesinclude tartaric acid and its salts (e.g., sodium tartrate and potassiumtartrate). In some examples, the activator can include alkali metalhydroxides, such as sodium hydroxide and potassium hydroxide. Furtherexamples of suitable activators include metasilicates (e.g., sodiummetasilicate and potassium metasilicate); carbonates (e.g., sodiumcarbonate and potassium carbonate); aluminates (e.g., sodium aluminateand potassium aluminate); and sulfates (e.g., sodium sulfate andpotassium sulfate). In some examples, the activator includes citricacid, tartaric acid, or mixtures thereof. In some examples, theactivator includes sodium hydroxide. In some examples, the activatorincludes a mixture of citric acid and sodium hydroxide. In examplesincluding a mixture of citric acid and sodium hydroxide, the weightratio of citric acid present in the mixture to sodium hydroxide presentin the mixture is from 0.4:1 to 2.0:1, 0.6:1 to 1.9:1, 0.8:1 to 1.8:1,0.9:1 to 1.7:1, or 1.0:1 to 1.6:1. The activator components can bepre-mixed prior to being added to the other reactive components in theinorganic polymer or added separately to the other reactive components.For example, citric acid and sodium hydroxide could be combined toproduce sodium citrate and the mixture can include possibly one or moreof citric acid and sodium hydroxide in stoichiometric excess. In someembodiments, the activator includes a stoichiometric excess of sodiumhydroxide. The total amount of activators can include less than 95% byweight of citrate salts. For example, the total amount of activator caninclude from 25-85%, 30-75%, or 35-65% citrate salts by weight. Themixture in solution and the mixture when combined with the reactivepowder can have a pH of from 12 to 13.5 or about 13.

The activator can be present as a reactant in an amount of from 1.5% to8.5% dry weight based on the weight of the reactive powder. For example,the activator can be present in an amount of from 2% to 8%, from 3% to7%, or from 4% to 6%. In some examples, the activator can be present inan amount of 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%,7.5%, 8% or 8.5% dry weight based on the weight of the reactive powder.For example, when sodium hydroxide and citric acid are used as theactivators, the amount of sodium hydroxide used in the activatorsolution can be from 0.3 to 15.6, 0.5 to 10, 0.75 to 7.5, or 1 to 5 dryparts by weight based on the weight of reactive powder and the amount ofcitric acid used in the activator solution can be from 0.25 to 8.5, 0.5to 0.7, 0.75 to 0.6, or 1 to 4.5 dry parts by weight based on the weightof reactive powder. The resulting activator solution can include sodiumcitrate and optionally one or more of citric acid or sodium hydroxide.

The activator can be provided, for example, as a solution. In someexamples, the activator can be provided in water as an aqueous solutionin a concentration of from 10% to 50% or from 20% to 40% based on theweight of the solution. For example, the concentration of the activatorin the aqueous solution can be from 25% to 35% or from 28% to 32% basedon the weight of the solution. Examples of suitable concentrations forthe activator in the aqueous solution include 10%, 15%, 20%, 25%, 30%,35%, 40%, 45%, or 50% based on the weight of the solution.

The inorganic polymer compositions described herein are prepared in thepresence of aerating agents, including blowing agents and foamingagents. Examples of suitable blowing agents include aluminum powder,perborates (e.g., sodium perborate), peroxides (e.g., H₂O₂ or an organicperoxide), and chloride dioxide. The blowing agent can be present in anamount of from 0.1% to 10% by weight of the reactive powder. Theaerating agents described herein can also include foaming agents. Insome examples, the foaming agent can be an air-entraining agent. Foamingagents can be used to help the system maintain air or other gases, e.g.,from the mixing process. The foaming agents can include non-ionicsurfactants, anion surfactants, and/or cationic surfactants. Examples ofsuitable foaming agents include sodium alkyl ether sulfate, ammoniumalkyl ether sulfate, sodium alpha olefin sulfonate, sodium decethsulfate, ammonium deceth sulfate, sodium laureth sulfate, and sodiumdodecylbenzene sulfonate. The foaming agents can be provided in anamount of 0.1% or less based on the weight of the reactive powder. Insome examples, the foaming agents can be included in the compositions inan amount of from 0.001% by weight to 0.1% by weight or from 0.005% byweight to 0.05% by weight (e.g., 0.01% by weight).

The reactants to form the inorganic polymer compositions are reacted inthe presence of water. The water can be provided in the reactive mixtureby providing the activator in solution and/or by adding water directlyto the reactive mixture. The solution to binder or solution to reactivepowder weight ratio (i.e., the ratio of the solution including activatorto reactive powder) can be from 0.09:1 to 0.5:1, depending on theproduct being made and the process being used for producing the product.

The reactants used to form the inorganic polymer compositions canfurther include a retardant. Retardants are optionally included toprevent the composition from stiffening too rapidly, which can result ina reduction of strength in the structure. Examples of suitableretardants for inclusion as reactants include borax, boric acid, gypsum,phosphates, gluconates, or a mixture of these. In some examples, theretardant is present in an amount of from 0.4% to 7.5% based on theweight of the reactive powder.

The cementitious material can include a filler, such as those describedherein. In some examples, the cementitious material can include a rapidset cement, Portland cement, and a filler such as fly ash, slag, sand,or combinations thereof. In some embodiments, the cementitious materialcan include a rapid set cement and a filler such as fly ash, slag, orsand. In some examples, the cementitious material can include Portlandcement and a filler. In some examples, the cementitious materialconsists or consists essentially of a rapid set cement, a filler in anamount of 30% or less by weight (e.g., 25% or less by weight, or 20% orless by weight), based on the total weight of the cementitious material,and optionally Portland cement. In some examples, the filler (e.g., flyash, slag, sand, or combinations thereof) can be present in an amount offrom 5% to 30% by weight, based on the total weight of the cementitiousmaterial. In some examples, the filler can include a lightweight filler.

In some embodiments, a cementitious material can include a fibermaterial, e.g., to provide increased strength, stiffness or toughness.In some examples, fire resistant or retardant glass fibers can beincluded to impart fire resistance or retarding properties to thecementitious material. Suitable fiber materials useful with thecementitious material are described herein. The fibers can be includedin an amount of 0.1% to 6% based on the weight of the cementitiousmaterial.

Additional components useful with the cementitious material describedherein include air entraining agents, water reducers, plasticizers,pigments, anti-efflorescence agents, ultraviolet light stabilizers,retardants including fire retardants, antimicrobials, and antioxidants.Air entraining agents can be used to entrain air in the cementitiousmaterial thereby reducing the density of the cementitious material.Water reducers can be included in the compositions described herein toreduce the amount of water in the composition while maintaining theworkability, fluidity, and/or plasticity of the composition. In someexamples, the water reducer is a high-range water reducer, such as, forexample, a superplasticizer admixture. Examples of suitable waterreducers include lignin, naphthalene, melamine, polycarboxylates,lignosulfates and formaldehyde condensates (e.g., sodium naphthalenesulfonate formaldehyde condensate). Water reducers can be provided in anamount of from greater than 0 to 1% by weight based on the weight of thecementitious material.

The cementitious material can further include a photocatalyst.Photocatalysts are optionally included for the reduction of nitrogenoxides (NOx) and self-cleaning. In some embodiments, the cementitiousmaterial can include titanium dioxide. Example of suitable photocatalystincludes titanium dioxide. In some embodiments, the photocatalyst can bedispersed within the cementitious material. In some embodiments, thephotocatalyst can be present as a coating on the cementitious material.In some examples, the titanium dioxide can be provided as a coating onthe cementitious material and is present in an amount of from 1% to 10%based on the weight of the coating on the cementitious material.

The cementitious material can be any suitable thickness to confer adesirable property to the composite panel, e.g., to provide increasedstrength, handleability, stiffness or toughness. In some embodiments,the thickness of the cementitious material can be 0.5 inch or less. Forexample, the cementitious material can have an average thickness of 0.4inch or less, 0.3 inch or less, 0.25 inch or less, 0.20 inch or less, or0.15 inch or less. In some embodiments, the cementitious material canhave an average thickness of 0.005 inch or greater, 0.01 inch orgreater, 0.05 inch or greater, or 0.1 inch or greater. In someembodiments, the cementitious layer can have an average thickness offrom 0.005 inch to 0.25 inch or from 0.005 inch to 0.20 inch.

In some embodiments, the fiber material (including the fiberreinforcement), the cementitious material, and/or the particulate fillersuch as fly ash can be coated with a composition to modify theirreactivity. For example, the fiber material, the cementitious material,and/or the particulate filler can be coated with a sizing agent such asa coupling agent (compatibilizer). In some embodiments, the fibermaterial, the cementitious material, and/or the particulate filler canbe coated with a composition for promoting adhesion. U.S. Pat. No.5,064,876 to Hamada et al. and U.S. Pat. No. 5,082,738 to Swofford, forexample, disclose compositions for promoting adhesion. U.S. Pat. No.4,062,999 to Kondo et al. and U.S. Pat. No. 6,602,379 to Li et al.describe suitable aminosilane compounds for coating fibers. In someembodiments, the fiber material, the cementitious material, and/or theparticulate filler are surface coated with a composition comprising asilane compound such as aminosilane. In some embodiments, the fibermaterial, the cementitious material, and/or the particulate filler aresurface coated with a composition comprising an oil, starch, or acombination thereof.

As described herein, the composite panel can include a first fiberreinforcement on a first surface of the foam stock and a second fiberreinforcement on a second surface, opposite the first surface, of thefoam stock. In some embodiments, the composite panel can include a firstfiber reinforcement on a first surface of the foam stock and a material,other than a fiber reinforcement, on a second surface of the foam stock.In some embodiments, the material can include a cementitious layer, apaper sheet, a metal sheet, a polymeric layer, or a combination thereof.Suitable materials that can be included on the second surface of thefoam stock include an aluminum sheet, an aluminum-plated sheet, a zincsheet, a zinc-plated sheet, an aluminum/zinc alloy sheet, analuminum/zinc alloy-plated sheet, a stainless steel sheet, craft paper,a polymeric surfacing film, or a combination thereof.

Methods

Methods of preparing the polyurethane or polyisocyanurate foam stocksare described herein. Methods of preparing the composite panels are alsodescribed herein. The foam stocks can be produced using a batch,semi-batch, or continuous process. In some embodiments, the method caninclude forming a polyurethane or polyisocyanurate mixture. Thepolyurethane or polyisocyanurate mixture can be produced by mixing theone or more isocyanates, the one or more polyols, and the filler in amixing apparatus. The materials can be added in any suitable order. Forexample, in some embodiments, the mixing stage of the method used toprepare the foam stock can include: (1) mixing the polyol and filler;(2) mixing the isocyanate with the polyol, and filler; and optionally(3) mixing the catalyst with the isocyanate, the polyol, and the filler.

The polyurethane or polyisocyanurate mixture can be blended in anysuitable manner to obtain a homogeneous or heterogeneous blend of theone or more isocyanate, the one or more polyols, the filler, and thecatalyst. In some embodiments, mixing can be conducted in a high speedmixer or an extruder. The method can include applying shear to themixture to disperse the filler in the mixture. An ultrasonic device canbe used for enhanced mixing and/or wetting of the various components ofthe composite. The ultrasonic device produces an ultrasound of a certainfrequency that can be varied during the mixing and/or extrusion process.The ultrasonic device useful in the preparation of composite panelsdescribed herein can be attached to or adjacent to the extruder and/ormixer. For example, the ultrasonic device can be attached to a die ornozzle or to the port of the extruder or mixer. An ultrasonic device mayprovide de-aeration of undesired gas bubbles and better mixing for theother components, such as blowing agents, surfactants, and catalysts.

The method of making the foam stock can include allowing the one or moreisocyanates and the one or more polyols to react in the presence of thefiller to form a polyurethane or polyisocyanurate foam having a firstsurface and a second surface opposite the first surface. The curingstage of the method used to prepare the foam stock can be carried out ina mold cavity of a mold, the mold cavity formed by at least an interiormold surface. The mold can include individual batch molds such as acardboard box. The cardboard box can work as a protective materialduring handling of the mold in the plant. In some embodiments, a moldedarticle can then be formed prior to the additional method steps informing the composite panel.

The polyurethane or polyisocyanurate mixture can be applied to the moldusing a nozzle traversing the mold. In some embodiments, the one or morepolyols, one or more isocyanates, or a mixture thereof, and the fillercan be included in amounts, which result in a workable viscosity(initial viscosity) of 100,000 cPs or less for the polyurethane orpolyisocyanurate mixture, and thus improves the processability of suchmaterials and products. In some embodiments, the mixture can be appliedto the mold at a viscosity of from 5,000 to 100,000 cPs or from 20,000to 100,000 cPs at the temperature of the mixture. The viscosity of thecomposite mixture can be measured using a Brookfield Viscometer.

In some embodiments, the polyurethane or polyisocyanurate mixture can befoamed. The method of making the polyurethane or polyisocyanurate foamscan include allowing the mixture to expand via a gas phase to form afoam having a first surface and a second surface opposite the firstsurface. The gas phase can be generated in situ from reaction of waterwith the one or more isocyanates. The gas can be introduced into thepolyurethane mixture. Suitable gases are known in the art. In someembodiments, the gas can be captured after gelation (i.e., formation) ofthe foam.

The foaming action of the polyurethane or polyisocyanurate foams can bedescribed as having a “cream time,” during which foaming is initiatedand the mixture reaches a consistency of a soft creamy foam, a “firmtime” at which the foam sets up and hardens, and a “tack free time” atwhich time surface no longer feels sticky. The cream time of thepolyisocyanurate or polyurethane can be 20 seconds or longer, 40 secondsor longer, 60 seconds or longer, or 80 seconds or longer. For example,the cream time of the polyisocyanurate or polyurethane can be from 20seconds to 120 seconds, from 40 seconds to 120 seconds, from 60 secondsto 120 seconds or from 80 seconds to 120 seconds. The tack free time ofthe polyisocyanurate or polyurethane can be 90 seconds or longer, 2minutes or longer, 3 minutes or longer, 4 minutes or longer, or 5minutes or longer and/or 7 minutes or less, 6 minutes or less, 5 minutesor less, or 4 minutes or less. For example, the tack free time of thepolyisocyanurate or polyurethane can be from 90 seconds to 7 minutes,from 2 minutes to 7 minutes or from 3 minutes to 6 minutes. In someembodiments, the polyisocyanurate or polyurethane foam reaches ahardness of 20 shore D at no less than 5 minutes. For example, thepolyisocyanurate or polyurethane foam does not reach a hardness of 20shore D in less than 5 minutes. For example, the polyurethane foam doesnot reach a hardness of 20 shore D in less than 7.5 minutes, less than10 minutes, less than 12.5 minutes, less than 15 minutes, less than 17.5minutes, or less than 20 minutes. The Shore D hardness can be determinedusing a durometer as described in ASTM D2240.

In some cases, the mixture can be allowed to rise freely during foamingin the mold. After the polyurethane or polyisocyanurate foam is formed,the method can include removing the foam stock from the mold. Asdescribed herein, the mold can be a flexible, disposable container. Insome embodiments, the method can include cutting through the containerto remove the foam stock from the mold.

Once the foam stock is removed from the mold, it can be trimmed toremove the bottom skin from the mold and the crown of the foam stock orbun that forms from the free rise of the foam. For example, the foamstock can be cut using a horizontal blade into a plurality ofpolyurethane or polyisocyanurate foam units having predeterminedthicknesses. The polyurethane or polyisocyanurate foam thickness can befrom 0.1 inch to 6 inches. For example, the polyurethane orpolyisocyanurate foam can have a thickness of 0.1 inch to 4 inches, 0.1inch to 3 inches, 0.1 inch to 2 inches, or 0.125 inch to 1 inch.

Composite panels can be produced from the cut polyurethane orpolyisocyanurate foam units. The method can include applying a firstfiber reinforcement to a surface of the foam. In some embodiments, thefiber reinforcement can be applied to the foam before it has completelycured, such that at least a portion of the fiber reinforcement becomesembedded in the foam. For example, the fiber reinforcement can beapplied to the polyurethane or polyisocyanurate mixture after themixture is fed to the mold. In some embodiments, the fiber reinforcementcan be applied to the mold prior to the mixture being fed into the moldand can become embedded prior to the full curing of the mixture. In someembodiments, the fiber reinforcement can be applied to the foam afterthe polyurethane or polyisocyanurate has been cured. For example, anadhesive can be applied to bond the fiber reinforcement to the foam. Theadhesive can be applied by spray coating, curtain coating, brushing,roller coating, dip coating, spin coating, or flow coating. Suitableadhesives include an adhesive derived from ethylene vinyl acetate,acrylic, urethane, epoxy, starch, gum, resin (such as gum arabic, gumtragacanth, rubber or shellac), or combinations thereof.

The method can further include applying a cementitious material to thefiber reinforcement. The cementitious material can be in the form of acementitious slurry. The cementitious slurry can be applied by rollercoating, curtain coating, dip coating, brushing, with a trowel, orspraying. In some embodiments, the application of the cementitiousmaterial can be vacuum assisted. In some embodiments, the method caninclude applying the cementitious slurry to the fiber reinforcement,after applying the fiber reinforcement to the foam. In some embodiments,the cementitious material and the fiber reinforcement can be applied tothe foam simultaneously. For example, the method can include applying acementitious slurry to the fiber reinforcement prior to applying thefiber reinforcement to the foam. In this example, at least a portion ofthe fiber reinforcement becomes embedded in the cementitious material.

In some embodiments, the method can include applying the cementitiousslurry to the foam, prior to applying the fiber reinforcement to thefoam.

The method of making the composite panels can include applying anadhesive to the fiber reinforcement or the foam prior to applying thecementitious material to facilitate bonding of the cementitiousmaterial. The adhesive can be applied by spray coating, curtain coating,brushing, roller coating, dip coating, spin coating, or flow coating.Suitable adhesives are described herein.

In some embodiments, the method can include applying a water and/orwater vapor barrier prior to applying the cementitious material. Forexample, the adhesive can produce a water and/or water vapor barrier.Alternatively, a water and/or water vapor barrier film or other materialcan be applied prior to applying the cementitious material.

In some embodiments, the cementitious material, the first fiberreinforcement, and the foam are directly adhered without the use of anadhesive layer. In embodiments wherein the cementitious slurry and thefirst fiber reinforcement are directly bonded to a fly ash-filled foam,it has been discovered that the cementitious slurry forms mechanicalbonds with the fly ash present in the foam thereby enhancing the bondingof the cementitious slurry and the first fiber reinforcement to thefoam.

In some embodiments, the method can include applying a liquid to asurface of the foam to activate the cementitious slurry. In certainembodiments, the liquid can be an aqueous solution having a pH of 5 orgreater or 6.5 or greater. The liquid optionally includes an activator.Suitable activators are described herein.

In some embodiments, incorporation of the fiber reinforcement and/or thecementitious layer onto the filled foam can maintain similar or improvedphysical properties and mechanical performance such as flexuralstrength, hardness, stiffness, flame resistance, and handleability ofsuch materials, when the fiber reinforcement and/or the cementitiouslayer is excluded from or included in minor amounts in the foam. Theoptimization of various properties of the composite panels, such ashardness, stiffness, flexural strength, handleability, and flameresistance of the foams allows their use in building materials and otherstructural applications. For example, the composite panels can be formedinto shaped articles and used in building materials. Suitable buildingmaterials include building panels, tile backer board, sheathing, roofingproducts, siding materials, sheets, sound barrier/insulation, thermalbarriers, insulation, decking materials, fencing materials, cladding, orother shaped articles. Examples of shaped articles made using thecomposite panels described herein include roof tiles such as roof tileshingles, roof cover boards, slate panels, shake panels, cast moldedproducts, moldings, sills, stone, masonry, brick products, posts, signs,guard rails, retaining walls, park benches, tables, slats, cornerarches, columns, wall boards, ceiling tiles, ceiling boards, soffits, orrailroad ties.

In some embodiments, incorporation of the fiber reinforcement on thefilled foam to form the composite panels can increase the flexuralstrength of the foam, compared to a foam without the fiberreinforcement. In some embodiments, the flexural strength of the foamcan be increased by at least 10%, for example, 15% or greater, 20% orgreater, 25% or greater, 30% or greater, 35% or greater, 50% or greater,75% or greater, or even 100% or greater, compared to a foam without thefiber reinforcement. The flexural strength of the composite panelsdescribed herein can be 200 psi or greater (e.g., up to 1600 psi). Forexample, the flexural strength of the composite panels can be 300 psi orgreater, 500 psi or greater, 700 psi or greater, 900 psi or greater,1000 psi or greater, 1100 psi or greater, 1200 psi or greater, 1300 psior greater, 1400 psi or greater, or 1500 psi or greater. The flexuralstrength can be determined by the load required to fracture arectangular prism loaded in the three point bend test as described inASTM C1185-08 (2012).

In some embodiments, incorporation of the fiber reinforcement and thecementitious layer on the filled polyurethane foam can increase thehardness of the foam, compared to a composite without the fiberreinforcement and the cementitious layer. In some embodiments, the ShoreD hardness of the composite panels described herein can be 50 or greater(e.g., up to 90). For example, the Shore D hardness of the compositepanels can be 55 or greater, 60 or greater, 65 or greater, 75 orgreater, or 80 or greater. The Shore D hardness can be determined usinga durometer as described in ASTM D2240.

In some embodiments, incorporation of the fiber reinforcement and thecementitious layer on the foam can increase the stiffness of thecomposite, compared to a composite without the fiber reinforcement andthe cementitious layer. In some embodiments, the modulus of elasticity(stiffness) of the composite panel can be 10 ksi or greater, 50 ksi orgreater or 100 ksi or greater. For example, the modulus of elasticitycan be from 10 to 500 ksi or from 50 to 500 ksi. The modulus ofelasticity can be determined as described in ASTM C947-03.

In some embodiments, incorporation of the fiber reinforcement and thecementitious layer on the filled foam can increase the flame resistanceof the composite, compared to a composite without the fiberreinforcement and the cementitious layer. In some embodiments, thecomposite panels can be qualified as a Class A material in the ASTM E84tunnel test. In some embodiments, the composite panels have a flamespread rating of 25 or less and a smoke development rating of 450 orless. The flame spread and smoke development ratings can be determinedas described in the ASTM E84 test.

EXAMPLES

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thecompounds, compositions, articles, devices and/or methods claimed hereinare made and evaluated, and are intended to be purely exemplary and arenot intended to limit the scope of the disclosure. Unless indicatedotherwise, parts and percentages are on a weight basis, temperature isin ° C. or is at ambient temperature, and pressure is at or nearatmospheric.

Mechanical Properties of Filled Polyurethane Foams.

Preparation of polyurethane foams: Polyurethane foams were preparedusing three different polyols labeled as Polyol A, a petroleum-derivedpolypropylene based polyol having a hydroxyl number of 240 mg KOH/g, afunctionality of 3, and a viscosity of 250 mPa·s; Polyol B, a glycerininitiated polyether polyol having a hydroxyl number of 240 mg KOH/g, afunctionality of 3, and a viscosity of 250 mPa·s at 25° C.; and PolyolC, a sucrose/amine initiated polyether polyol having a hydroxyl numberof 350 mg KOH/g, a functionality of 5.5, and a viscosity of 2,500 mPa·sat 25° C.

The composites were prepared by wetting fly ash and 1/8″ chopped fiberglass in an extruder with concurrent streams of polyol (about 12% byweight of the foam) and methylene diphenyl diisocyanate (about 13% byweight of the foam) and optionally a catalyst and simultaneouslystirring began. The mixture was extruded into a cardboard box andallowed to freely rise and cure. The physical properties of thecomposites, including flexural strength, density, handleability,extension, and modulus were determined. The handleability is a measureof the ability of the material to be flexed during use and is calculatedas 0.5× breaking load×ultimate deflection/thickness of the testspecimen. The extension is a measure of the deflection of a sampleduring the three point bend test as defined in ASTM C947-03. The modulusis calculated from the stress/strain curve of the three point bend test.Normalized flexural strength is the ratio of flexural strength dividedby the density.

TABLE 2 Components and mechanical properties of filled polyurethanefoams: Foam #1 Foam #2 Foam #3 Polyol Polyol Polyol Polyol A B C Polyolconc. (wt %) 17% 19% 14% Isocyanate conc. (wt %) 13% 14% 13.4%  Surfactant Silicone-based Surfactant conc. (wt %) 0.16%   Fiber glassconc. (wt %)  1%  4%  5% Filler conc. (wt %) 69% 66% 68% Catalyst conc.(pphp) 0.2 0.1 Water conc. (wt %) 0.17%   0.31%   0.11%   Viscosity(cPs) 7590 35000 72300 (77° F.) (80° F.) (85° F.) Cream time (sec) 11585 41 Tack-free time (sec) 240 140 375 Density (pcf) 21.7 17.0 22.6Modulus (ksi) 31.6 15.0 26.5 Flexural strength (psi) 413 352 271Extension (in.) 0.041 0.089 0.611 Handleability 4.02 7.69 7.43

Summary: As shown in Table 2, the polyurethane foams prepared usingPolyols A-C produced foams having suitable density, modulus, flexuralstrength, extension, and handleability. The cream time for the threesamples was 41 seconds up to 115 seconds. The tack-free time was from140 seconds up to 375 seconds.

The compositions and methods of the appended claims are not limited inscope by the specific compositions and methods described herein, whichare intended as illustrations of a few aspects of the claims and anycompositions and methods that are functionally equivalent are intendedto fall within the scope of the claims. Various modifications of thecompositions and methods in addition to those shown and described hereinare intended to fall within the scope of the appended claims. Further,while only certain representative materials and method steps disclosedherein are specifically described, other combinations of the materialsand method steps also are intended to fall within the scope of theappended claims, even if not specifically recited. Thus, a combinationof steps, elements, components, or constituents may be explicitlymentioned herein; however, other combinations of steps, elements,components, and constituents are included, even though not explicitlystated. The term “comprising” and variations thereof as used herein isused synonymously with the term “including” and variations thereof andare open, non-limiting terms. Although the terms “comprising” and“including” have been used herein to describe various embodiments, theterms “consisting essentially of” and “consisting of” can be used inplace of “comprising” and “including” to provide for more specificembodiments and are also disclosed. As used in this disclosure and inthe appended claims, the singular forms “a”, “an”, “the”, include pluralreferents unless the context clearly dictates otherwise.

1-57. (canceled)
 58. A composite panel comprising: a foam stockcomprising a recycled filler, wherein the recycled filler is present inan amount equal to or greater than 10% by weight, based on the totalweight of the foam stock; and a cementitious coating on the foam stock;wherein the foam stock has a density of 10 g/cm³ to 35 g/cm³; andwherein a compressive strength of the foam stock is equal to or greaterthan 100 psi.
 59. The composite panel of claim 58, wherein a thicknessof the composite panel is equal to or less than 2 inches.
 60. Thecomposite panel of claim 58, wherein a thickness of the cementitiouscoating is equal to or less than 0.5 inches.
 61. The composite panel ofclaim 58, wherein a width of the composite panel is 2 feet to 4 feet.62. The composite panel of claim 58, wherein the foam stock comprisespolyurethane in an amount of 1% to 50% by weight, based on the totalweight of the foam stock.
 63. The composite panel of claim 58, whereinthe recycled filler is present in an amount equal to or greater than 30%by weight, based on the total weight of the foam stock.
 64. Thecomposite panel of claim 58, wherein the foam stock, the cementitiouscoating, or both further comprises a plurality of fibers dispersedtherein.
 65. The composite panel of claim 64, wherein the fibers arepresent in the foam stock, the cementitious coating, or both in anamount of 0.25% to 15% by weight, based on the total weight of therespective foam stock, the cementitious coating, or both.
 66. Thecomposite panel of claim 64, wherein an average length of the fibers is1 mm to 12 mm.
 67. The composite panel of claim 58, wherein thecomposite panel comprises two cementitious coatings on opposite surfacesof the foam stock.
 68. The composite panel of claim 58, wherein thecomposite panel is a Class A material in the ASTM E84 tunnel test. 69.The composite panel of claim 58, wherein a flame spread rating of thecomposite panel is equal to or less than
 25. 70. The composite panel ofclaim 58, wherein a smoke development rating of the composite panel isequal to or less than
 450. 71. A title backer board, sound barrier, orroofing panel comprising the composite panel of claim
 58. 72. Acomposite panel comprising: a foam stock comprising a recycled filler,wherein the recycled filler is present in an amount equal to or greaterthan 10% by weight, based on the total weight of the foam stock; whereinthe foam stock has a density of 10 g/cm³ to 25 g/cm³; wherein acompressive strength of the foam stock is equal to or greater than 100psi; and wherein a thickness of the composite panel is 1 inch to 4inches.
 73. The composite panel of claim 72, wherein the foam stockcomprises polyurethane in an amount of 1% to 50% by weight, based on thetotal weight of the foam stock.
 74. A method of making a polyurethane orpolyisocyanurate foam, comprising: mixing one or more isocyanatesselected from the group consisting of diisocyanates, polyisocyanates,and mixtures thereof, one or more polyols; and a filler to produce amixture, wherein the filler is present in an amount from greater than50% to 90% by weight, based on the total weight of the mixture; applyingthe mixture to a mold; and allowing the mixture to react and expand toform the polyurethane or polyisocyanurate foam; wherein the mixtureapplied to the mold has a tack free time of from 90 seconds to 7minutes; and wherein the resulting polyurethane or polyisocyanurate foamhas a density of 10 lb/ft³ or greater.
 75. The method of claim 74,wherein the mixture applied to the mold has a cream time of from 20seconds to 120 seconds.
 76. The method of claim 74, wherein the mixtureis applied to the mold at a viscosity of 20,000 cPs to 100,000 cPs atthe temperature of the mixture.